CN115050979A - High-performance porous PtCu @ PWO for hydrogen fuel cell device x Oxygen reduction catalyst - Google Patents
High-performance porous PtCu @ PWO for hydrogen fuel cell device x Oxygen reduction catalyst Download PDFInfo
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- CN115050979A CN115050979A CN202210446051.1A CN202210446051A CN115050979A CN 115050979 A CN115050979 A CN 115050979A CN 202210446051 A CN202210446051 A CN 202210446051A CN 115050979 A CN115050979 A CN 115050979A
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 24
- 239000001301 oxygen Substances 0.000 title claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000446 fuel Substances 0.000 title claims abstract description 23
- 239000001257 hydrogen Substances 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 4
- 239000002159 nanocrystal Substances 0.000 claims abstract 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 150000001879 copper Chemical class 0.000 claims description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000003057 platinum Chemical class 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical group [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 7
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 6
- 239000011964 heteropoly acid Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims 3
- 238000006722 reduction reaction Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 15
- 229910052697 platinum Inorganic materials 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 239000011943 nanocatalyst Substances 0.000 abstract description 3
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
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Abstract
The invention discloses a high-performance porous PtCu @ PWO for an actual hydrogen fuel cell device x An oxygen reduction catalyst characterized by: the catalyst is porous PtCu @ PWO x The nano alloy composite material is a porous nano crystal with a natural carrier, has uniform size of about 7.95nm, wherein the content of Pt is 20-50%, the content of Cu is 50-80%, and the range of X is 60-70%. Porous PtCu @ PWO x The mass activity of the nano alloy composite material in acid oxygen reduction is 3.94A mg ‑1 Area activity of 3.3mA cm ‑2 Which is 26.3 times/13.7 times of that of commercial carbon-supported platinum respectively, and is a nano catalyst with highest oxygen reduction reaction quality activity under acidic conditions by the platinum-copper base.
Description
Technical Field
The invention relates to a high-performance porous PtCu @ PWO for a hydrogen fuel cell device x An oxygen reduction catalyst and a synthetic method.
Background
With the acceleration of the global energy production decarbonization movement, hydrogen is increasingly being regarded as a clean and environmentally friendly energy source, which is expected to play a key role. Hydrogen-fueled Proton Exchange Membrane Fuel Cells (PEMFCs) are of great interest for their high energy conversion efficiency and zero carbon emissions. Platinum is the most active noble metal electrocatalyst in oxygen reduction reactions, but its large-scale application is limited by its scarcity of reserves, high price, activity and poor durability. In order to reduce the use of noble metals, reduce the cost of noble metals and prepare nano-catalysts with better catalytic activity and durability, the catalytic activity and the stability can be improved by adding cheap transition metals (such as copper, cobalt, nickel and iron) and platinum to form alloys.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: preparation of porous PtCu @ PWO in organic solvent x The synthesis method of the nano alloy composite material is simple and easy to repeat, has uniform appearance and size, and has excellent catalytic performance and stability in acid oxygen reduction reaction and actual room temperature hydrogen fuel cells.
The technical scheme of the invention is as follows: high-performance porous PtCu @ PWO for hydrogen fuel cell device x An oxygen reduction catalyst, wherein the catalyst is porous PtCu @ PWO x A nano alloy composite material. The appearance is novel, the size is uniform, and the particle size is about 7.95 nm; wherein the content of Pt is 20-50%, the content of Cu is 50-80%, and the range of X is 60-70%.
High-performance porous PtCu @ PWO for practical hydrogen fuel cell device x The synthesis of the oxygen reduction catalyst comprises the following steps: (1) adding a surfactant Cetyl Trimethyl Ammonium Bromide (CTAB), a reducing agent ascorbic acid and heteropoly acid phosphotungstic acid hydrate into a mixed solution of an organic solvent N, N-dimethylacetamide and formaldehyde together with platinum salt and copper salt, and stirring for 10-15 minutes at room temperature; (2) transferring the mixed solution obtained in the step (1) into a high-pressure reaction kettle to react for 6-10 hours, and controlling the temperature to be 120-170 ℃; (3) cooling the product obtained in the step (2) to room temperature, washing, and performing centrifugal separation to obtain the porous PtCu @ PWO x The nano alloy composite material is prepared, and the sample is dispersed and stored in ethanol.
The platinum salt in the step (1) is platinum acetylacetonate, and the copper salt is copper acetylacetonate.
The dosage of the metal platinum salt is unchanged, the dosage of the copper salt is 0.0305mmol-0.1222mmol, and the molar ratio of the platinum salt to the copper salt precursor is 1:1-1: 3.
The porous PtCu @ PWO x The application of the nano alloy composite material in the cathode oxygen reduction reaction of the actual hydrogen fuel cell.
The invention has the beneficial effects that: adopts a hydrothermal synthesis method to synthesize porous PtCu @ PWO under the condition of adding heteropoly acid phosphotungstic acid hydrate x The nano alloy composite material has a particle size of about 7.95 nm. The crystal configuration of the crystal is face-centered cubic through testing X-ray diffraction spectrum. Porous PtCu @ PWO x The mass activity of the nano alloy composite material in acid oxygen reduction is 3.94A mg -1 Area activity of 3.3mA cm -2 The catalyst is 26.3 times/13.7 times of commercial carbon-supported platinum respectively, and is a nano catalyst with highest oxygen reduction reaction quality activity under acidic conditions by the platinum-copper base. Porous PtCu @ PWO after 20,000 cycles of accelerated stability testing x The mass activity of the nano alloy composite material is reduced by 17.8 percent, while the mass activity of the commercial carbon-supported platinum is reduced by 40 percent. Porous PtCu @ PWO in a practical hydrogen fuel cell at room temperature x The power density of the nano alloy composite material is 218.6mW cm -2 1.66 times that of commercial carbon supported platinum. Porous PtCu @ PWO was also tested for accelerated stability at 20,000 cycles x The power density of the nano-alloy composite material decreased only 21.7%, while the commercial carbon supported platinum decreased 34.3%.
Porous PtCu @ PWO synthesized by the method x The nano alloy composite material has special shape, novel structure, excellent catalytic performance in the actual hydrogen fuel cell and good stability, and has the possibility of replacing the current commercial carbon platinum-carrying catalyst.
Drawings
FIG. 1 is a porous PtCu @ PWO x A transmission electron microscope observation result graph of the nano alloy composite material;
FIG. 2 is a diagram of porous PtCu @ PWO x A scanning electron microscope observation result graph and an element distribution graph of the nano alloy composite material;
FIG. 3 is a porous PtCu @ PWO x An X-ray diffraction result graph of the nano alloy composite material;
FIG. 4 is a porous PtCu @ PWO x Nano-alloy composite and commercial carbonA graph comparing catalytic performance and stability of platinum-loaded oxygen reduction;
FIG. 5 is a porous PtCu @ PWO x The power density and stability of the nano-alloy composite material and commercial carbon supported platinum in an actual hydrogen fuel cell device at room temperature are compared.
Detailed Description
Example 1:
high-performance porous PtCu @ PWO for hydrogen fuel cell device x The synthesis of the oxygen reduction catalyst comprises the following steps:
(1) adding 36.4mg of surfactant Cetyl Trimethyl Ammonium Bromide (CTAB), 20mg of reducing agent ascorbic acid and 30mg of heteropoly acid phosphotungstic acid hydrate, 12mg of platinum acetylacetonate and 24mg of copper acetylacetonate into a mixed solution of 7mL of N, N-dimethylacetamide and 1mL of formaldehyde organic solvent together with copper salt and platinum salt, wherein the using amount of copper salt metal is 0.0915mmol, the molar ratio of platinum salt to copper salt precursor is 1:3, and stirring for 10-15 minutes at room temperature;
(2) transferring the mixed solution obtained in the step (1) to a high-pressure reaction kettle to react for 8 hours, and controlling the temperature at 150 ℃;
(3) cooling the product obtained in the step (2) to room temperature, washing, and performing centrifugal separation to obtain the porous PtCu @ PWO x The nano alloy composite material is prepared, and the sample is dispersed and stored in ethanol.
Example 2:
high-performance porous PtCu @ PWO for hydrogen fuel cell device x The synthesis of the oxygen reduction catalyst comprises the following steps:
(3) adding 36.4mg of surfactant Cetyl Trimethyl Ammonium Bromide (CTAB), 20mg of reducing agent ascorbic acid and 30mg of heteropoly acid phosphotungstic acid hydrate, 12mg of platinum acetylacetonate and 16mg of copper acetylacetonate into a mixed solution of 7mL of N, N-dimethylacetamide and 1mL of formaldehyde in an organic solvent, wherein the dosage of copper salt metal is 0.061mmol, the molar ratio of the platinum salt to the copper salt precursor is 1:2, and stirring for 10-15 minutes at room temperature;
(4) transferring the mixed solution obtained in the step (1) into a high-pressure reaction kettle to react for 8 hours, and controlling the temperature at 150 ℃;
(3) cooling the product obtained in the step (2) to room temperature, washing, and performing centrifugal separation to obtain the porous PtCu @ PWO x The nano alloy composite material is prepared, and the sample is dispersed and stored in ethanol.
Example 3:
high-performance porous PtCu @ PWO for hydrogen fuel cell device x The synthesis of the oxygen reduction catalyst comprises the following steps:
(5) adding 36.4mg of surfactant Cetyl Trimethyl Ammonium Bromide (CTAB), 20mg of reducing agent ascorbic acid and 30mg of heteropoly acid phosphotungstic acid hydrate, 12mg of platinum acetylacetonate and 8mg of copper acetylacetonate into a mixed solution of 7mL of N, N-dimethylacetamide and 1mL of formaldehyde organic solvent, wherein the using amount of copper salt metal is 0.0305mmol, the molar ratio of the platinum salt to a copper salt precursor is 1:1, and stirring at room temperature for 10-15 minutes;
(6) transferring the mixed solution obtained in the step (1) to a high-pressure reaction kettle to react for 8 hours, and controlling the temperature at 150 ℃;
(3) cooling the product obtained in the step (2) to room temperature, washing, and performing centrifugal separation to obtain the porous PtCu @ PWO x The nano alloy composite material is prepared, and the sample is dispersed and stored in ethanol.
Reverse example 1
(1) Sequentially adding 0.025mmol of chloroplatinic acid, 20mg of copper acetylacetonate and 400mg of surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) into 10mL of oleylamine, and performing ultrasonic treatment for 30 minutes to obtain a uniform solution;
(2) the clear solution obtained in step (1) was transferred to a 25mL autoclave. Quickly preheating to 170 ℃, and terminating the reaction after 8 hours;
(3) centrifuging the product obtained in the step (2), and washing 3 times by using a 50:50 ethanol/deionized water mixture.
As can be seen by comparison with the reverse example 1, the mass activity of the PtCu nano-framework in the reverse example in oxygen reduction was 0.82A mg -1 After 10,000 circles of accelerated durability test, the mass activity is reduced by 70%, compared with the porous PtCu @ PWO obtained by the experiment x Activity of nano alloy composite materialBoth the properties and stability were lower, and the PtCu nano-frame in the reverse example was not tested for an actual hydrogen fuel cell.
Reverse example 2
(1) Dispersing 194mg of platinum acetylacetonate, 130mg of copper acetylacetonate and 300mg of Ketjen black carbon in 100mL of acetone, and performing ultrasonic treatment for 1 hour to obtain a suspension;
(2) magnetically stirring the suspension obtained in the step (1) at room temperature for 1 hour, and then drying the mixture by using a rotary evaporator device;
(3) putting the metal precursor dried in the step (2) in a tube furnace at 500 ℃ NH 3 Annealing for 2 hours in a flowing atmosphere to obtain a nitrogen-doped disordered PtCu sample (marked as D-PtCuN/KB);
(4) D-PtCuN/KB obtained in the step (3) is in flowing H 2 /Ar(5％H 2 ) Under the conditions, annealing is carried out for 1 hour at the temperature of 800 ℃, and an ordered intermetallic compound PtCu sample (Int-PtCuN/KB) is formed.
As can be seen by comparison with the reverse example 2, the mass activity of the ordered intermetallic compound PtCu sample in the reverse example in acidic oxygen reduction was 1.15A mg -1 After 20,000 circles of accelerated stability test, the quality activity is reduced by 23.5 percent, compared with the porous PtCu @ PWO obtained in the experiment x The activity and stability of the nano-alloy composite was lower and the ordered intermetallic compound PtCu sample in the reverse example was not tested for an actual hydrogen fuel cell.
Claims (6)
1. An oxygen reduction catalyst for a hydrogen fuel cell device, characterized by: the catalyst is porous PtCu @ PWO x The X range of the nano alloy composite material is 60-70%.
2. An oxygen reduction catalyst for a hydrogen fuel cell device according to claim 1, characterized in that: the PtCu @ PWO x The alloy is a porous nanocrystal with a natural support, uniform in size, about 7.95nm, with a Pt content of 20-50% and a Cu content of 50-80%.
3. A method of synthesizing an oxygen reduction catalyst for a hydrogen fuel cell device according to claim 2, wherein: the method comprises the following steps: (1) adding a surfactant Cetyl Trimethyl Ammonium Bromide (CTAB), a reducing agent ascorbic acid and heteropoly acid phosphotungstic acid hydrate into a mixed solution of an organic solvent N, N-dimethylacetamide and formaldehyde together with platinum salt and copper salt, and stirring for 10-15 minutes at room temperature; (2) transferring the mixed solution obtained in the step (1) to a high-pressure reaction kettle to react for 6-10 hours, and controlling the temperature to be 120-170 ℃; (3) cooling the product obtained in the step (2) to room temperature, washing, and performing centrifugal separation to obtain the porous PtCu @ PWO x The nano alloy composite material is prepared, and the sample is dispersed and stored in ethanol.
4. A method of synthesizing an oxygen reduction catalyst for a hydrogen fuel cell device in accordance with claim 3, wherein: the platinum salt in the step (1) is platinum acetylacetonate, and the copper salt is copper acetylacetonate.
5. A method of synthesizing an oxygen reduction catalyst for a hydrogen fuel cell device in accordance with claim 3, wherein: the dosage of the metal platinum salt is unchanged, the dosage of the copper salt is 0.0305mmol-0.1222mmol, and the molar ratio of the platinum salt to the copper salt precursor is 1:1-1: 3.
6. The porous PtCu @ PWO of any of claims 1-5 x The nano alloy composite material is used as a cathode catalyst in the application of actual hydrogen fuel cell devices.
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